CN113880136B - Zirconium tetrachloride and/or silicon tetrachloride, preparation method and preparation device thereof - Google Patents
Zirconium tetrachloride and/or silicon tetrachloride, preparation method and preparation device thereof Download PDFInfo
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000005049 silicon tetrachloride Substances 0.000 title claims abstract description 102
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 112
- 238000009835 boiling Methods 0.000 claims abstract description 77
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 66
- 239000010703 silicon Substances 0.000 claims abstract description 66
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 59
- 239000002699 waste material Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000004576 sand Substances 0.000 claims abstract description 45
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 44
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 43
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000005520 cutting process Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 239000002893 slag Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000007599 discharging Methods 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 20
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 5
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- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
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- 238000005265 energy consumption Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical compound C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10715—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides zirconium tetrachloride and/or silicon tetrachloride, a preparation method and a preparation device thereof. The method comprises the following steps: settling, press-filtering, drying and crushing waste silicon slurry generated in the cutting process of crystalline silicon to obtain recovered silicon powder with a first particle size; respectively crushing zircon sand and a carbon reducer to respectively obtain zircon sand and a carbon reducer with second particle sizes; mixing the recovered silicon powder, zircon sand and a carbon reducing agent, adding a binder, and granulating to obtain mixed raw material particles with a third particle size; raising the temperature in the boiling chlorination furnace to a first temperature, introducing chlorine into the boiling chlorination furnace, adding the obtained mixed raw material particles, and carrying out chlorination reaction to obtain a reaction product comprising zirconium tetrachloride and silicon tetrachloride; and cooling and separating the reaction product to obtain solid zirconium tetrachloride and liquid silicon tetrachloride. The preparation method of the invention realizes the full recycling of the silicon element lost in the cutting process of the crystalline silicon.
Description
Technical Field
The invention relates to zirconium tetrachloride and/or silicon tetrachloride, a preparation method and a preparation device thereof.
Background
In the slicing process of crystalline silicon (monocrystalline silicon or polycrystalline silicon), when a wire saw cuts a silicon rod, about 50% of the crystalline silicon enters into a cutting liquid in the form of silicon powder in the cutting process because the diameter of a steel wire is very close to the thickness of a silicon wafer, so that the loss of silicon element is caused. In addition, the temperature is higher in the cutting process, so that silicon powder is easily oxidized into silicon dioxide, and the waste silicon powder separated from the cutting waste liquid is inevitably contacted with air in the storage process, so that part of the silicon powder is easily oxidized into silicon dioxide, and the content of the silicon dioxide is further increased. Meanwhile, because the silicon carbide has high hardness, the silicon carbide can be adhered to a cutting line to be used as a cutting medium, and therefore, the silicon carbide can be added into the sand line cutting mortar as an additive to be added into the sand line. Therefore, this results in a relatively complex composition of the waste silicon powder, for example, containing elements such as silicon, oxygen, carbon, and metal impurities. In addition, the waste silicon powder has extremely fine particle size, large specific surface area and small density, so that the recovery difficulty of silicon element is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of zirconium tetrachloride and/or silicon tetrachloride for fully recycling waste silicon slurry generated in the cutting process of crystalline silicon, zirconium tetrachloride and/or silicon tetrachloride prepared by the preparation method and a preparation device thereof.
The technical scheme adopted for solving the technical problems of the invention is as follows:
a method for preparing zirconium tetrachloride and/or silicon tetrachloride, comprising the following steps:
step 1, settling, press filtering, drying and crushing waste silicon slurry generated in the cutting process of crystalline silicon to obtain recovered silicon powder with a first particle size;
step 2, respectively crushing zircon sand and a carbon reducer to respectively obtain zircon sand and a carbon reducer with a second particle size;
step 3, mixing the recovered silicon powder, zircon sand and a carbon reducing agent, adding water and a binder, and granulating to obtain mixed raw material particles with a third particle size;
step 4, raising the temperature in the boiling chlorination furnace to a first temperature, introducing chlorine into the boiling chlorination furnace, adding mixed raw material particles, and carrying out chlorination reaction to obtain a reaction product comprising zirconium tetrachloride and silicon tetrachloride; and
and 5, cooling and separating the reaction product to obtain solid zirconium tetrachloride and liquid silicon tetrachloride respectively.
Preferably, the method further comprises:
step 6, carrying out online deslagging at the temperature of 100-200 ℃ and discharging the high Wen Feizha generated by the boiling chlorination furnace,
the liquid silicon tetrachloride obtained in the step 5 is adopted to cool the high-temperature slag generated by the boiling chlorination furnace, and the liquid silicon tetrachloride is heated and vaporized and then enters the boiling chlorination furnace again.
Preferably, the first particle size is 100-300 mesh, the second particle size is 300-500 mesh, and the third particle size is 20-120 mesh.
Preferably, in step 1, the sedimentation is carried out by adding a flocculant to the waste silicon slurry, and the mass ratio of flocculant to the waste silicon slurry is (1-3): 100,
the waste silicon slurry filter cake obtained after filter pressing contains simple substance silicon, silicon dioxide, silicon carbide, diamond powder and a small amount of metal impurities, and
and drying the waste silicon slurry filter cake after filter pressing at the temperature of 150-200 ℃ and the pressure of 10-50 KPa.
Preferably, the flocculant is at least one of polyaluminum chloride, polyaluminum sulfate, polyaluminum ferric sulfate and polyaluminum chloride.
Preferably, in step 3, the mass ratio of zircon sand, carbon reducing agent, recovered silica powder is 183: (48-60): (28-84), and
the binder is at least one of sodium methylcellulose, cyanoacrylate and polyvinyl acetal, and the mass ratio of the binder, water and recovered silicon powder is (1-5): (5-15): 100.
preferably, in step 4, the first temperature is 1100-1200 ℃, and the reaction pressure of the chlorination reaction is 30-100KPa.
The preparation method of zirconium tetrachloride and/or silicon tetrachloride has the following beneficial effects:
the silicon element in the waste silicon slurry generated in the process of cutting the crystalline silicon is fully recycled, so that the waste of the silicon element is reduced; the recycling of silicon element in the crystalline silicon industrial chain is realized, and the environmental pollution is avoided; the silicon tetrachloride obtained by recycling the silicon element provides a silicon source for the production of the chlorosilane, and reduces the production cost of the chlorosilane. In addition, the chlorination reaction process for recycling the silicon powder provides reaction heat for the chlorination reactor, so that the energy consumption of the system is reduced. Meanwhile, the liquid silicon tetrachloride obtained by the chlorination reaction is used as a cooling medium, so that the temperature of an online deslagging pipeline is accurately controlled, and the safety in the online deslagging process is improved. In addition, the liquid silicon tetrachloride serving as a cooling medium is heated and vaporized and then enters the boiling chlorination furnace along the online slag discharge pipeline upstream again, and is cooled and separated again to obtain the liquid silicon tetrachloride, so that the recovery and recycling of the silicon tetrachloride are realized.
The invention also provides zirconium tetrachloride and/or silicon tetrachloride, which are prepared by the method.
The invention also provides a preparation device of zirconium tetrachloride and/or silicon tetrachloride, which comprises:
a boiling chlorination furnace for reacting zircon sand, a carbon reducing agent, recovered silicon powder and chlorine gas; and
and a cooling and separating device for cooling and separating the reaction product discharged from the boiling chlorination furnace after reaction.
Preferably, the preparation device further comprises corresponding equipment for settling, press filtering, drying and crushing waste silicon slurry generated in the process of cutting crystalline silicon to obtain recovered silicon powder.
Preferably, the preparation device further comprises crushing equipment for respectively crushing the zircon sand and the carbon reducing agent so as to respectively obtain the zircon sand and the carbon reducing agent with the second particle size.
Preferably, the preparation device also comprises an online deslagging system which comprises an online deslagging pipeline and a deslagging storage tank,
wherein the slag discharging storage tank is communicated with the boiling chlorination furnace through the online slag discharging pipeline, and
the online slag discharging pipeline is connected with a silicon tetrachloride inlet pipeline which is used for adding liquid silicon tetrachloride to the online slag discharging pipeline so as to cool the height Wen Feizha in the online slag discharging pipeline.
Drawings
FIG. 1 shows a flow chart of a process for the preparation of zirconium tetrachloride and/or silicon tetrachloride;
FIG. 2 shows a schematic diagram of a device for producing zirconium tetrachloride and/or silicon tetrachloride;
fig. 3 shows a flow chart for the preparation of zirconium tetrachloride and/or silicon tetrachloride and its on-line deslagging.
In the figure, 1 is a boiling chlorination furnace, 2 is a chlorine gas inlet pipeline, 3 is a solid mixture pipeline, 4 is a gas phase outlet pipeline, 5 is a reactor top pressure gauge, 6 is a reactor bottom pressure gauge, 7 is an online deslagging pipeline, 8 is a deslagging pipeline thermometer, 9 is a silicon tetrachloride inlet pipeline, 10 is a silicon tetrachloride regulating valve, 11 is a deslagging storage tank, 12 is a bottom deslagging port, 13 is a nitrogen replacement pipeline, and 14 is a top outlet tail gas pipeline.
Detailed Description
In order to better understand the technical solution of the present invention, the present invention will be further clearly and completely described in the following with reference to the drawings and specific embodiments of the present invention.
The slicing process of crystalline silicon (monocrystalline silicon or polycrystalline silicon) can cause serious loss of silicon element, silicon powder is easily oxidized into silicon dioxide at a high temperature in the cutting process, and waste silicon powder separated from cutting waste liquid is inevitably contacted with air in the storage process, so that part of silicon powder is easily oxidized into silicon dioxide, and the recovery difficulty of the silicon element is increased. Therefore, the invention provides a preparation method of zirconium tetrachloride and/or silicon tetrachloride capable of fully recycling waste silicon slurry generated in the cutting process of crystalline silicon, which comprises the following steps:
step 1, settling, press filtering, drying and crushing waste silicon slurry generated in the cutting process of crystalline silicon to obtain recovered silicon powder with a first particle size;
step 2, respectively crushing zircon sand and a carbon reducer to respectively obtain zircon sand and a carbon reducer with a second particle size;
step 3, mixing the recovered silicon powder, zircon sand and a carbon reducing agent, adding water and a binder, and granulating to obtain mixed raw material particles with a third particle size;
step 4, raising the temperature in the boiling chlorination furnace to a first temperature, introducing chlorine into the boiling chlorination furnace, adding mixed raw material particles, and carrying out chlorination reaction to obtain a reaction product comprising zirconium tetrachloride and silicon tetrachloride; and
and 5, cooling and separating the reaction product to obtain solid zirconium tetrachloride and liquid silicon tetrachloride respectively.
Accordingly, there is provided silicon tetrachloride and/or silicon tetrachloride, which is produced by the process described above.
Correspondingly, also provided is a preparation device of zirconium tetrachloride and/or silicon tetrachloride, comprising:
a boiling chlorination furnace for reacting zircon sand, a carbon reducing agent, recovered silicon powder and chlorine gas; and
and a cooling and separating device for cooling and separating the reaction product discharged from the boiling chlorination furnace after reaction.
Example 1
Referring to fig. 1 and 3, the embodiment provides a preparation method of zirconium tetrachloride and/or silicon tetrachloride, which comprises the following steps:
step 1, settling, press filtering, drying and crushing waste silicon slurry generated in the cutting process of crystalline silicon to obtain recovered silicon powder with a first particle size;
discharging supernatant after settling the waste silicon slurry, recycling, and performing filter pressing on solid-phase sediment at the lower part to obtain a silicon mud filter cake; and drying the silicon mud filter cake, and crushing the dried solid waste silicon material to obtain the recovered silicon powder with the first particle size.
Step 2, respectively crushing zircon sand and a carbon reducer to respectively obtain zircon sand and a carbon reducer with a second particle size;
step 3, mixing the recovered silicon powder, zircon sand and a carbon reducing agent, adding water and a binder, and granulating to obtain mixed raw material particles with a third particle size;
step 4, raising the temperature in the boiling chlorination furnace to a first temperature, introducing chlorine into the boiling chlorination furnace, adding mixed raw material particles, and carrying out chlorination reaction to obtain a reaction product comprising zirconium tetrachloride and silicon tetrachloride; and
and 5, cooling and separating the reaction product to obtain solid zirconium tetrachloride and liquid silicon tetrachloride respectively.
In this embodiment, the first particle size is 100-300 mesh, the second particle size is 300-500 mesh, and the third particle size is 20-120 mesh.
In step 1, the sedimentation is carried out by adding a flocculant to the waste silicon slurry, and the mass ratio of the flocculant to the waste silicon slurry is (1-3): 100. the waste silicon slurry filter cake obtained after the filter pressing contains simple substance silicon, silicon dioxide, silicon carbide, diamond powder and a small amount of metal impurities, and the waste silicon slurry filter cake obtained after the filter pressing is dried at the temperature of 150-200 ℃ and the pressure of 10-50KPa for 3-5h. The flocculant may be at least one of polyaluminum chloride, polyaluminum sulfate, polyaluminum ferric sulfate and polyaluminum chloride.
In the step 3, the mass ratio of zircon sand, carbon reducer and recovered silicon powder is 183: (48-60): (28-84), wherein the binder is at least one of sodium methyl cellulose, cyanoacrylate and polyvinyl acetal, and the mass ratio of the binder, water and recovered silicon powder is (1-5): (5-15): 100.
in step 4, since the waste silicon slurry generated in the cutting process contains elemental silicon, silicon dioxide, silicon carbide, diamond powder and a small amount of metal impurities, the following chemical reaction occurs in the boiling chlorination furnace:
reaction formula 1: si+2Cl 2 →SiCl 4 (exothermic)
Reaction formula 2: siO (SiO) 2 +2Cl 2 +2C→SiCl 4 +2CO
Reaction formula 3: siC+2Cl 2 →SiCl 4 +C
Reaction formula 4: zrSiO 4 +4C+4Cl 2 →ZrCl 4 +SiCl 4 +4CO
Wherein the first temperature is the reaction temperature of the chlorination reaction, the temperature range is 1100-1200 ℃, and the reaction pressure of the chlorination reaction is 30-100KPa. For example, in the present embodiment, in order to reach the reaction temperature (i.e., the first temperature), pure silicon powder having a particle size of 40 to 200 mesh may be added to react with chlorine gas during the furnace start-up stage, but is not limited thereto. The elemental C generated in reaction scheme 3 can be used as a reducing agent in reaction schemes 2 and 4, and the use of a carbon reducing agent can be reduced. In addition, the exothermic reaction of the reaction formula 1 provides reaction heat for the chlorination reaction in the boiling reaction furnace, so that pure silicon powder is not required to be added in the reaction process except in the furnace starting stage to provide reaction heat for the chlorination reaction, thereby reducing the energy consumption of the system.
In addition, during operation of the fluidizing chlorination furnace, a portion of the oxides in the zircon sand are converted into metal chlorides, which have a high boiling point and are in solid form in the reaction furnace, such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and the like. Along with the progress of the reaction, high-boiling point chloride continuously gathers in the chlorination furnace, and when the high-boiling point chloride in the chlorination furnace reaches a certain amount, the reaction effect of the boiling chlorination furnace can be influenced, so that in order to ensure the normal operation of the boiling chlorination furnace, the inert components are required to be discharged. If slag is discharged after the furnace is stopped, the production cost is greatly increased, and meanwhile, the production efficiency is reduced; if slag is discharged online, there is a great safety risk, on one hand, because the temperature of slag is up to above 1000 ℃, and on the other hand, because the chlorine environment is present in the system, almost all metal materials can react with chlorine at high temperature of 1000 ℃, and on this condition, it is difficult to realize online safe slag discharge.
Therefore, the preparation method of zirconium tetrachloride provided in this embodiment further includes:
step 6, carrying out online deslagging at the temperature of 100-200 ℃ and discharging the high Wen Feizha generated by the boiling chlorination furnace,
the liquid silicon tetrachloride obtained in the step 5 is adopted to cool the high Wen Feizha generated by the boiling chlorination furnace to 100-200 ℃, and the liquid silicon tetrachloride is heated and vaporized and then enters the boiling chlorination furnace again, so that cooling separation can be carried out again, and the recovery and recycling of the silicon tetrachloride are realized. Under the condition, the temperature of the online slag discharging pipeline is accurately controlled, and the safety in the online slag discharging process is improved.
The embodiment also provides zirconium tetrachloride and silicon tetrachloride which are respectively prepared by adopting the method.
Example 2
As shown in fig. 2, the present embodiment discloses a preparation apparatus of zirconium tetrachloride and/or silicon tetrachloride, comprising:
a fluidizing chlorination furnace 1 for reacting zircon sand, a carbon reducing agent, recovered silicon powder, and chlorine gas; and
and a cooling and separating device for cooling and separating the reaction product discharged from the boiling chlorination furnace after reaction.
In some embodiments, to achieve safe online deslagging of the boiling chlorination furnace, the preparation device may further comprise an online deslagging system comprising an online deslagging pipeline 7 and a deslagging storage tank 11, wherein the deslagging storage tank 11 is communicated with the boiling chlorination furnace 1 through the online deslagging pipeline 7, and wherein a silicon tetrachloride inlet pipeline 9 is connected to the online deslagging pipeline 7 and is used for introducing liquid silicon tetrachloride into the online deslagging pipeline 7 so as to cool the height Wen Feizha in the online deslagging pipeline 7. The top outlet tail gas line 14 of the slag discharge tank 11 is used for discharging toxic and harmful substances such as chlorine and silicon tetrachloride remaining in the waste slag. For example, a small amount of chlorine and silicon tetrachloride is carried out from the fluidizing chlorination furnace 1 with the slag, and a small amount of vaporized silicon tetrachloride is carried out by the slag while deslagging on line.
Preferably, the preparation device further comprises corresponding equipment (not shown in the figure) for settling, press-filtering, drying and crushing the waste silicon slurry generated in the process of cutting the crystalline silicon to obtain the recovered silicon powder.
Further preferably, the preparation device further comprises a crushing device for crushing zircon sand and a carbon reducing agent respectively to obtain zircon sand and a carbon reducing agent (not shown in the figure) with second particle sizes respectively.
The apparatus of this example can be used to prepare zirconium tetrachloride and/or silicon tetrachloride in the process of example 1.
Example 3
The embodiment discloses a preparation method of zirconium tetrachloride and/or silicon tetrachloride, which adopts the device in the embodiment 2, as shown in fig. 2 and 3, and comprises the following specific processes:
step 1, placing waste silicon slurry (cutting mortar) generated by cutting crystalline silicon into a sedimentation tank, adding a polyaluminium chloride flocculant (the mass ratio of the polyaluminium chloride flocculant to the waste silicon slurry is 2:100) for sedimentation, recovering supernatant fluid to obtain ethylene glycol, and performing filter pressing on bottom solid-phase sediment by adopting a plate-and-frame filter press to obtain a solid silicon mud filter cake; and (3) placing the solid silicon mud filter cake in a vacuum dryer, vacuum drying the silicon mud filter cake for 5 hours at the temperature of 180 ℃ and the pressure of 10KPa, and then crushing the dried silicon mud filter cake by adopting a jaw crusher to obtain recovered silicon powder with the average particle size of 100 meshes.
And 2, respectively crushing the zircon sand and the carbonaceous reducing agent in a ball mill to obtain fine particles of the zircon sand and the carbonaceous reducing agent with the second particle size, wherein the average particle size of the fine particles is 300 meshes.
Step 3, small-particle zircon sand, a carbonaceous reducing agent and recovered silicon powder are mixed according to the mass ratio of 183:48:84, adding water and a binder sodium carboxymethyl cellulose (the mass ratio of the sodium carboxymethyl cellulose to the water to the recovered silicon powder is 1:15:100), and granulating to obtain mixed raw material particles with the average particle size of 20 meshes.
Step 4, introducing high-temperature chlorine gas at 200 ℃ into the boiling chlorination furnace 1 through a chlorine gas inlet pipeline 2, adding pure silicon powder with the average particle size of 40 meshes into the boiling chlorination furnace 1 through a solid mixture pipeline 3, and performing chlorination reaction with the chlorine gas to release a large amount of heat so as to gradually increase the temperature in the boiling chlorination furnace 1; when the temperature in the reaction furnace rises to 1200 ℃ and the pressure is 100KPa, stopping adding pure silicon powder, and finishing starting the furnace; the mixed raw materials with the third grain size, which are obtained in the step 3 and contain zircon sand, carbonaceous reducing agent and recovered silicon powder, are added into the boiling chlorination furnace 1 through a solid mixture pipeline 3 for chlorination reaction, wherein the pressure difference between the bottom pressure and the top pressure of the chlorination reactor is controlled to be in the range of 5-20KPa according to the readings of a reactor top pressure gauge 5 and a reactor bottom pressure gauge 6, and the pressure difference between the bottom pressure and the top pressure depends on the amount of the mixed raw materials with the third grain size, which are added into the boiling chlorination furnace 1 (for example, the pressure difference is increased when the proportion of the recovered silicon powder in the mixed raw materials with the third grain size is large, and the pressure difference is decreased when the proportion of the recovered silicon powder is small). The zircon sand, the carbonaceous reducing agent and the recovered silicon powder in the embodiment have the following mass ratio of 183:48:84, the pressure difference is preferably 15KPa.
And 5, cooling and separating the gas product obtained by the chlorination reaction from the gas phase outlet pipeline 4 into a cooling and separating device (not shown in fig. 2) at the rear end, cooling to 331 ℃ to obtain a solid zirconium tetrachloride product, and separating at 57.6 ℃ to obtain a liquid silicon tetrachloride product.
Step 6, after the boiling chlorination furnace 1 reacts for 36 hours, a plurality of high-boiling solid metal chloride salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like are accumulated in the boiling chlorination furnace 1, so that the reaction efficiency gradually decreases, online deslagging is needed, the temperature of an online deslagging pipeline 7 of the boiling chlorination furnace 1 is set to 150 ℃, a valve of the online deslagging pipeline 7 is slowly opened for online deslagging, a high Wen Feizha discharged from the bottom of the boiling chlorination furnace 1 enters the online deslagging pipeline 7 to enable the temperature of the deslagging pipeline to rise (namely, the temperature is higher than 150 ℃, the deslagging pipeline is displayed by a deslagging pipeline thermometer 8), a temperature cascade loop control system (not shown in fig. 2) is connected between the deslagging pipeline thermometer 8 and a silicon tetrachloride regulating valve 10 (shown by a dotted connecting line in fig. 2), the opening of the silicon tetrachloride regulating valve 10 is gradually increased under the control action of the temperature cascade loop control system, the liquid silicon tetrachloride (liquid silicon tetrachloride obtained from step 5) entering the online deslagging pipeline 7 is in an increased through a silicon tetrachloride inlet pipeline 9, the liquid silicon tetrachloride is in contact with high-temperature waste residues, so that the temperature of the liquid silicon tetrachloride is rapidly reduced, the liquid silicon tetrachloride is subjected to heat change into a gas phase, and the liquid silicon tetrachloride is recycled to be recycled and recycled in the boiling chlorination furnace 1, and the boiling chlorination furnace can be recycled, and cooled down again, and the liquid silicon chloride is recycled; when the temperature in the online slag discharging pipeline 7 is lower than 150 ℃ (displayed by the slag discharging pipeline thermometer 8), the opening of the silicon tetrachloride regulating valve 10 is gradually reduced until the silicon tetrachloride regulating valve is closed under the control action of the temperature cascade loop control system, so that the temperature in the online slag discharging pipeline 7 is always controlled to be about 150 ℃, and the safety of an online slag discharging process is ensured. After the waste residues enter the slag discharge storage tank 11 through the online slag discharge pipeline 7, an outlet tail gas pipeline 14 of the slag discharge storage tank 11 is opened, a nitrogen replacement pipeline 13 is opened to input nitrogen, the gas in the slag discharge storage tank 11 is replaced by the input nitrogen for 3 hours, residual toxic and harmful substances such as chlorine and silicon tetrachloride in the waste residues are removed, a top outlet tail gas pipeline 14 is closed, a nitrogen replacement pipeline 13 is closed, a bottom slag discharge port 12 is opened, and the waste residues in the storage tank are discharged and packaged.
Example 4
The embodiment discloses a preparation method of zirconium tetrachloride and/or silicon tetrachloride, which adopts the device in the embodiment 2, as shown in fig. 2 and 3, and comprises the following specific processes:
step 1, placing waste silicon slurry generated by cutting crystalline silicon into a sedimentation tank, adding a polymeric aluminum sulfate flocculant (the mass ratio of the polymeric aluminum sulfate flocculant to the waste silicon slurry is 1:100) for sedimentation, recovering supernatant fluid to obtain ethylene glycol, and performing filter pressing on bottom solid-phase sediment by adopting a plate-and-frame filter press to obtain a solid silicon mud filter cake; and (3) placing the solid silicon mud filter cake in a vacuum dryer, vacuum drying the silicon mud filter cake for 3 hours at the temperature of 200 ℃ and the pressure of 50KPa, and then crushing the dried silicon mud filter cake by adopting a jaw crusher to obtain recovered silicon powder with the average particle size of 220 meshes.
And 2, respectively crushing the zircon sand and the carbonaceous reducing agent in a ball mill to obtain fine particles of the zircon sand and the carbonaceous reducing agent with the second particle size, wherein the average particle size of the fine particles is 450 meshes.
Step 3, small-particle zircon sand, a carbonaceous reducing agent and recovered silicon powder are mixed according to the mass ratio of 183:60:50, adding water and a binder cyanoacrylate (the mass ratio of the cyanoacrylate, the water and the recovered silicon powder is 5:9:100), and granulating to obtain mixed raw material particles with the average particle size of 90 meshes.
Step 4, introducing high-temperature chlorine gas with the temperature of 200 ℃ into the boiling chlorination furnace 1 through a chlorine gas inlet pipeline 2, adding pure silicon powder with the average particle size of 200 meshes into the boiling chlorination furnace 1 through a solid mixture pipeline 3, and performing chlorination reaction with the chlorine gas to release a large amount of heat so as to gradually increase the temperature in the boiling chlorination furnace 1; when the temperature in the reaction furnace rises to 1155 ℃ and the pressure is 30KPa, stopping adding pure silicon powder, and finishing starting the furnace; the mixed raw materials with the third grain size, which are obtained in the step 3 and contain zircon sand, carbonaceous reducing agent and recovered silicon powder, are added into the boiling chlorination furnace 1 through a solid mixture pipeline 3 for chlorination reaction, wherein the pressure difference between the bottom pressure and the top pressure of the chlorination reactor is controlled to be in the range of 5-20KPa according to the readings of a reactor top pressure gauge 5 and a reactor bottom pressure gauge 6, and the pressure difference between the bottom pressure and the top pressure depends on the amount of the mixed raw materials with the third grain size, which are added into the boiling chlorination furnace 1 (for example, the pressure difference is increased when the proportion of the recovered silicon powder in the mixed raw materials with the third grain size is large, and the pressure difference is decreased when the proportion of the recovered silicon powder is small). The zircon sand, the carbonaceous reducing agent and the recovered silicon powder in the embodiment have the following mass ratio of 183:60:50, preferably the pressure difference is 10KPa.
And 5, cooling and separating the gas product obtained by the chlorination reaction from the gas phase outlet pipeline 4 into a cooling and separating device (not shown in fig. 2) at the rear end, cooling to 331 ℃ to obtain a solid zirconium tetrachloride product, and separating at 57.6 ℃ to obtain a liquid silicon tetrachloride product.
Step 6, after the boiling chlorination furnace 1 reacts for 36 hours, a plurality of high-boiling solid metal chloride salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like are accumulated in the boiling chlorination furnace 1, so that the reaction efficiency gradually decreases, online deslagging is needed, the temperature of an online deslagging pipeline 7 of the boiling chlorination furnace 1 is set to 200 ℃, a valve of the online deslagging pipeline 7 is slowly opened for online deslagging, a high Wen Feizha discharged from the bottom of the boiling chlorination furnace 1 enters the online deslagging pipeline 7 to enable the temperature of the deslagging pipeline to rise (namely, the temperature is higher than 200 ℃, the temperature is displayed by a deslagging pipeline thermometer 8), a temperature cascade loop control system (not shown in fig. 2) is connected between the deslagging pipeline thermometer 8 and a silicon tetrachloride regulating valve 10 (shown by a dotted connecting line in fig. 2), the opening of the silicon tetrachloride regulating valve 10 is gradually increased under the control action of the temperature cascade loop control system, the liquid silicon tetrachloride (liquid silicon tetrachloride obtained from step 5) entering the online deslagging pipeline 7 is in an increased through a silicon tetrachloride inlet pipeline 9, the liquid silicon tetrachloride is contacted with high-temperature waste residues to enable the temperature of the liquid silicon tetrachloride to rapidly decrease, the temperature of the waste residues to be changed into a gas phase, and the liquid silicon tetrachloride is recycled to be recycled and recycled in the boiling chlorination furnace 1, and the boiling chlorination furnace can be cooled again, and recycled; when the temperature in the online slag discharging pipeline 7 is lower than 200 ℃ (displayed by the slag discharging pipeline thermometer 8), the opening of the silicon tetrachloride regulating valve 10 is gradually reduced until the silicon tetrachloride regulating valve is closed under the control action of the temperature cascade loop control system, so that the temperature in the online slag discharging pipeline 7 is always controlled to be about 200 ℃, and the safety of an online slag discharging process is ensured. After the waste residues enter the slag discharge storage tank 11 through the online slag discharge pipeline 7, an outlet tail gas pipeline 14 of the slag discharge storage tank 11 is opened, a nitrogen replacement pipeline 13 is opened to input nitrogen, the gas in the slag discharge storage tank 11 is replaced by the input nitrogen for 3 hours, residual toxic and harmful substances such as chlorine and silicon tetrachloride in the waste residues are removed, a top outlet tail gas pipeline 14 is closed, a nitrogen replacement pipeline 13 is closed, a bottom slag discharge port 12 is opened, and the waste residues in the storage tank are discharged and packaged.
Example 5
The embodiment discloses a preparation method of zirconium tetrachloride and/or silicon tetrachloride, which adopts the device in the embodiment 2, as shown in fig. 2 and 3, and comprises the following specific processes:
step 1, placing waste silicon slurry generated by cutting crystalline silicon into a sedimentation tank, adding a polymeric ferric chloride flocculant (the mass ratio of the polymeric ferric chloride flocculant to the waste silicon slurry is 3:100) for sedimentation, recovering supernatant fluid to obtain ethylene glycol, and performing filter pressing on bottom solid-phase sediment by adopting a plate-and-frame filter press to obtain a solid silicon mud filter cake; and (3) placing the solid silicon mud filter cake in a vacuum dryer, vacuum drying the silicon mud filter cake for 4 hours at the temperature of 150 ℃ and the pressure of 25KPa, and then crushing the dried silicon mud filter cake by adopting a jaw crusher to obtain recovered silicon powder with the average particle size of 300 meshes.
And 2, respectively crushing the zircon sand and the carbonaceous reducing agent in a ball mill to obtain fine particles of the zircon sand and the carbonaceous reducing agent with the second particle size, wherein the average particle size of the fine particles is 500 meshes.
Step 3, small-particle zircon sand, a carbonaceous reducing agent and recovered silicon powder are mixed according to the mass ratio of 183:53:28, adding water and a binder polyvinyl acetal (the mass ratio of the polyvinyl acetal to the water to the recovered silicon powder is 3:5:100) for granulation, and obtaining mixed raw material particles with the average particle size of 120 meshes.
Step 4, introducing high-temperature chlorine gas at 200 ℃ into the boiling chlorination furnace 1 through a chlorine gas inlet pipeline 2, adding pure silicon powder with the average particle size of 150 meshes into the boiling chlorination furnace 1 through a solid mixture pipeline 3, and performing chlorination reaction with the chlorine gas to release a large amount of heat so as to gradually increase the temperature in the boiling chlorination furnace 1; when the temperature in the reaction furnace rises to 1100 ℃ and the pressure is 70KPa, stopping adding pure silicon powder, and finishing starting the furnace; the mixed raw materials with the third grain size, which are obtained in the step 3 and contain zircon sand, carbonaceous reducing agent and recovered silicon powder, are added into the boiling chlorination furnace 1 through a solid mixture pipeline 3 for chlorination reaction, wherein the pressure difference between the bottom pressure and the top pressure of the chlorination reactor is controlled to be in the range of 5-20KPa according to the readings of a reactor top pressure gauge 5 and a reactor bottom pressure gauge 6, and the pressure difference between the bottom pressure and the top pressure depends on the amount of the mixed raw materials with the third grain size, which are added into the boiling chlorination furnace 1 (for example, the pressure difference is increased when the proportion of the recovered silicon powder in the mixed raw materials with the third grain size is large, and the pressure difference is decreased when the proportion of the recovered silicon powder is small). The zircon sand, the carbonaceous reducing agent and the recovered silicon powder in the embodiment have the following mass ratio of 183:53:28, preferably the pressure difference is 5KPa.
And 5, cooling and separating the gas product obtained by the chlorination reaction from the gas phase outlet pipeline 4 into a cooling and separating device (not shown in fig. 2) at the rear end, cooling to 331 ℃ to obtain a solid zirconium tetrachloride product, and separating at 57.6 ℃ to obtain a liquid silicon tetrachloride product.
Step 6, after the boiling chlorination furnace 1 reacts for 36 hours, a plurality of high-boiling solid metal chloride salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like are accumulated in the boiling chlorination furnace 1, so that the reaction efficiency gradually decreases, online deslagging is needed, the temperature of an online deslagging pipeline 7 of the boiling chlorination furnace 1 is set to 100 ℃, a valve of the online deslagging pipeline 7 is slowly opened for online deslagging, a high Wen Feizha discharged from the bottom of the boiling chlorination furnace 1 enters the online deslagging pipeline 7 to enable the temperature of the deslagging pipeline to rise (namely, the temperature is higher than 100 ℃, the deslagging pipeline is displayed by a deslagging pipeline thermometer 8), a temperature cascade loop control system (not shown in fig. 2) is connected between the deslagging pipeline thermometer 8 and a silicon tetrachloride regulating valve 10 (shown by a dotted connecting line in fig. 2), the opening of the silicon tetrachloride regulating valve 10 is gradually increased under the control action of the temperature cascade loop control system, the liquid silicon tetrachloride (liquid silicon tetrachloride obtained from step 5) entering the online deslagging pipeline 7 is in an increased through a silicon tetrachloride inlet pipeline 9, the liquid silicon tetrachloride is in contact with high-temperature waste residues, so that the temperature of the liquid silicon tetrachloride is rapidly reduced, the liquid silicon tetrachloride is subjected to heat change into a gas phase, and the liquid silicon tetrachloride is recycled to be recycled and recycled in the boiling chlorination furnace 1, and the boiling chlorination furnace can be recycled, and cooled down again, and the liquid silicon chloride is recycled; when the temperature in the online slag discharging pipeline 7 is lower than 100 ℃ (displayed by the slag discharging pipeline thermometer 8), the opening of the silicon tetrachloride regulating valve 10 is gradually reduced until the silicon tetrachloride regulating valve is closed under the control action of the temperature cascade loop control system, so that the temperature in the online slag discharging pipeline 7 is always controlled to be about 100 ℃, and the safety of an online slag discharging process is ensured. After the waste residues enter the slag discharge storage tank 11 through the online slag discharge pipeline 7, an outlet tail gas pipeline 14 of the slag discharge storage tank 11 is opened, a nitrogen replacement pipeline 13 is opened to input nitrogen, the gas in the slag discharge storage tank 11 is replaced by the input nitrogen for 3 hours, residual toxic and harmful substances such as chlorine and silicon tetrachloride in the waste residues are removed, a top outlet tail gas pipeline 14 is closed, a nitrogen replacement pipeline 13 is closed, a bottom slag discharge port 12 is opened, and the waste residues in the storage tank are discharged and packaged.
The method of the embodiment 3 to the embodiment 5 realizes the full recycling of the silicon element in the crystalline silicon cutting waste, and reduces the waste of the silicon element; the recycling of silicon element in the crystalline silicon industrial chain is realized, and the environmental pollution is avoided; the silicon tetrachloride obtained by recycling the silicon element provides a low-cost silicon source for the production of the chlorosilane, and reduces the production cost of the chlorosilane. In addition, the chlorination reaction process for recycling the silicon powder provides reaction heat for the chlorination reactor, so that the energy consumption of the system is reduced. Meanwhile, the liquid silicon tetrachloride obtained by the chlorination reaction is used as a cooling medium, so that the temperature of a slag discharge pipeline is accurately controlled, and the safety in the online slag discharge process is improved. In addition, the liquid silicon tetrachloride serving as a cooling medium is heated and vaporized and then enters the boiling chlorination furnace along the online slag discharge pipeline upstream again, so that the silicon tetrachloride is recovered and recycled.
The embodiments of the present invention are not limited to the embodiments shown in the detailed description, and those skilled in the art, based on the technical solution of the present invention, may derive other embodiments, which also belong to the technical scope of the present invention.
Claims (7)
1. A method for preparing zirconium tetrachloride and/or silicon tetrachloride, comprising the following steps:
step 1, settling, press filtering, drying and crushing waste silicon slurry generated in the cutting process of crystalline silicon to obtain recovered silicon powder with a first particle size;
step 2, respectively crushing zircon sand and a carbon reducer to respectively obtain zircon sand and a carbon reducer with a second particle size;
step 3, mixing the recovered silicon powder, zircon sand and a carbon reducing agent, adding water and a binder, and granulating to obtain mixed raw material particles with a third particle size;
step 4, raising the temperature in the boiling chlorination furnace to a first temperature, introducing chlorine into the boiling chlorination furnace, adding mixed raw material particles, and carrying out chlorination reaction to obtain a reaction product comprising zirconium tetrachloride and silicon tetrachloride, wherein the pressure difference between the bottom pressure and the top pressure of the chlorination reactor is controlled to be within the range of 5-20KPa, and in order to reach the first temperature, adding pure silicon powder to react with the chlorine in the furnace starting stage, and providing reaction heat for the chlorination reaction in the boiling reaction furnace; and
step 5, cooling and separating the reaction product to obtain solid zirconium tetrachloride and liquid silicon tetrachloride respectively;
step 6, carrying out online deslagging at the temperature of 100-200 ℃, discharging the height Wen Feizha generated by the boiling chlorination furnace, specifically, introducing the height Wen Feizha discharged from the bottom of the boiling chlorination furnace into an online deslagging pipeline, introducing liquid silicon tetrachloride into the online deslagging pipeline,
the liquid silicon tetrachloride obtained in the step 5 is adopted to cool the high-temperature slag generated by the boiling chlorination furnace to 100-200 ℃, and the liquid silicon tetrachloride is heated and vaporized and then enters the boiling chlorination furnace again.
2. The method of claim 1, wherein the first particle size is 100-300 mesh, the second particle size is 300-500 mesh, and the third particle size is 20-120 mesh.
3. The production method according to claim 1, wherein in step 1, the sedimentation is carried out by adding a flocculant to the waste silicon slurry, and a mass ratio of the flocculant to the waste silicon slurry is (1-3): 100,
the waste silicon slurry filter cake obtained after filter pressing contains simple substance silicon, silicon dioxide, silicon carbide, diamond powder and a small amount of metal impurities, and
and drying the waste silicon slurry filter cake after filter pressing at the temperature of 150-200 ℃ and the pressure of 10-50 KPa.
4. The method according to claim 3, wherein the flocculant is at least one of polyaluminum chloride, polyaluminum sulfate, polyferric sulfate and polyferric chloride.
5. The method according to claim 1, wherein in step 3, the mass ratio of zircon sand, carbon reducing agent, and recovered silicon powder is 183: (48-60): (28-84), and
the binder is at least one of sodium methylcellulose, cyanoacrylate and polyvinyl acetal, and the mass ratio of the binder, water and recovered silicon powder is (1-5): (5-15): 100.
6. the method according to claim 1, wherein in step 4, the first temperature is 1100 to 1200 ℃, and the reaction pressure of the chlorination reaction is 30 to 100KPa.
7. A production apparatus for zirconium tetrachloride and/or silicon tetrachloride for the production process as claimed in any one of claims 1 to 6, comprising:
the fluidized bed chlorination furnace (1) is used for enabling zircon sand, a carbon reducing agent and recovered silicon powder to react with chlorine, specifically, a chlorine inlet pipeline (2) and a solid mixture pipeline (3) are arranged on the fluidized bed chlorination furnace, the chlorine inlet pipeline (2) is used for introducing high-temperature chlorine gas with the temperature of 200 ℃ into the fluidized bed chlorination furnace, the solid mixture pipeline (3) is used for adding pure silicon powder into the fluidized bed chlorination furnace, and a great amount of heat is released by chlorination reaction with the chlorine gas so that the temperature in the fluidized bed chlorination furnace is gradually increased until the furnace is started, after the adding of fine silicon powder is stopped, the mixed raw materials containing zircon sand, the carbon reducing agent and the recovered silicon powder are added for chlorination reaction; and
a cooling and separating device for cooling and separating the reaction product discharged from the boiling chlorination furnace after reaction;
an online deslagging system comprises an online deslagging pipeline (7) and a deslagging storage tank (11),
wherein the slag discharging storage tank (11) is communicated with the boiling chlorination furnace (1) through the online slag discharging pipeline (7),
and, be connected with silicon tetrachloride import pipeline (9) on online slag removal pipeline (7), it is used for adding liquid silicon tetrachloride to online slag removal pipeline (7) to the high Wen Feizha in online slag removal pipeline (7) is cooled down.
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| WO2011078225A1 (en) * | 2009-12-22 | 2011-06-30 | Jnc株式会社 | Method for manufacturing polysilicon and method for manufacturing silicon tetrachloride |
| CN104556226A (en) * | 2015-01-07 | 2015-04-29 | 赤峰盛森硅业科技发展有限公司 | Method for producing zirconium tetrachloride |
| CN104891560A (en) * | 2015-05-19 | 2015-09-09 | 成都易态科技有限公司 | Producing process and equipment for crude titanium tetrachloride |
| CN205773416U (en) * | 2016-05-26 | 2016-12-07 | 宜宾天原集团股份有限公司 | The device of the chlorination legal system titanium dioxide of continuously-running |
| CN106865552A (en) * | 2016-10-26 | 2017-06-20 | 东北大学 | A kind of method that high-purity silicon powder is reclaimed in cutting waste material slurry from crystalline silicon |
| CN208700597U (en) * | 2018-07-19 | 2019-04-05 | 新特能源股份有限公司 | A kind of boiling chloridizing furnace |
| CN108726568A (en) * | 2018-08-23 | 2018-11-02 | 新特能源股份有限公司 | The purifier and method of zirconium chloride synthesis gas |
| CN110902718A (en) * | 2018-09-14 | 2020-03-24 | 新疆晶硕新材料有限公司 | Improved zirconium tetrachloride preparation method and zirconium tetrachloride |
| CN210065203U (en) * | 2019-03-20 | 2020-02-14 | 锦州旭日新材料科技有限公司 | System for producing refined zirconium tetrachloride by ball-making zirconium silicate boiling chlorination method |
| CN110240196A (en) * | 2019-07-31 | 2019-09-17 | 辽宁华祥新材料有限公司 | The method and zirconium chloride of zirconium chloride are prepared using zircon sand fluidizing chlorination method |
| CN110357110A (en) * | 2019-07-31 | 2019-10-22 | 锦州中特电炉有限公司 | A method of silicon tetrachloride is produced with polysilicon slice silicon powder |
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